Disazo compounds containing a piperazinylethysulfonyl group

ABSTRACT

A compound of the formula (1) ##STR1## or a salt thereof wherein J is a group of the formula (1a) ##STR2## and A, Y, T, T 1 , R, R 1 , R 4 , R 5  and R 6  are as defined in the specification are useful as black colorants for ink jet printing inks.

This application is the national phase of international applicationPCT/GB97/00482 filed Feb. 21, 1997 which designated the U.S.

This invention relates to a coloured bisazo compound and aqueoussolutions thereof suitable for use in the coloration of substrates,especially sheet materials such as paper, and especially by a printingprocess such as ink jet printing.

According to the present invention there is provided a compound ofFormula (1) or a salt thereof: ##STR3## wherein: J is a group of theFormula (1a): ##STR4## wherein: ##STR5## wherein

    ______________________________________                                        R.sup.2 & R.sup.3                                                                   each independently is H, --COOH or --SO.sub.3 H;                          Z.sup.1 & Z.sup.5 each independently is H, optionally substituted                 alkyl, optionally                                                          substituted alkoxy or --NZ.sup.3 Z.sup.4 ;                                   Z.sup.2 is H, halo, --COOH, --SO.sub.3 H, --OH, optionally substituted              alkyl, optionally substituted alkoxy or optionally substituted                alkylthio;                                                              Z.sup.3 is H or optionally substituted alkyl;                                 Z.sup.4 is H, optionally substituted alkyl or acyl;                           R.sup.1 is H, optionally substituted alkyl, alkylcarbonyl, alkylsulphony          l,                                                                         alkoxycarbonyl, alkoxysulphonyl, arylcarbonyl or arylsulphonyl;                   T & T.sup.1 each independently is H or --SO.sub.3 H;                     R is H, optionally substituted alkyl, optionally substituted aryl,                  or a group --B--NQ.sup.1 Q.sup.2 ;                                      B is optionally substituted C.sub.2-6 -alkylene; and                          Q.sup.1 & each independently is H, optionally substituted C.sub.1-4               -alkyl or                                                                 Q.sup.2 Q.sup.1 and Q.sup.2 together with the N atom to which they are            attached                                                                   form an optionally substituted 5- or 6-membered ring.                      ______________________________________                                    

When A is phenylene it is preferably phen-1,3-ylene or phen-1,4-yleneand when A is naphthylene it is preferably naphth-1,4-ylene ornaphth-1,5-ylene.

When A is substituted it preferably carries from one to three,especially one or two substituents, preferably in the 2-, 3-, 4-, 2,4-,3,4-, 2,5- or 3,5- positions when A is phenylene or in the 4-, 5-, 6-,7-, 8-, 4,5-, 4,8-, 5,8-, or 6,7- positions when A is naphthyleneSubstituents on A are preferably selected from:

--COOH; --SO₃ H; --OH; --CN; --NO₂ ; --PO(OH)₂ ; --B(OH)₂ ;

halo, preferably --Cl;

alkyl, preferably C₁₋₄ -alkyl and especially methyl;

alkoxy, preferably C₁₋₄ -alkoxy and especially methoxy;

--SO₂ R⁷, --COOR⁷, --SO₂ R⁷ or --COR⁷, wherein R⁷ is optionallysubstituted C₁₋₄ --alkyl or optionally substituted aryl, especiallyphenyl; and

acylamino, especially alkyl- or aryl-carbonylamino or alkyl- oraryl-sulphonylamino, and more especially C₁₋₄ -alkyl-CONH--or C₁₋₄-alkyl-SO₂ NH--.

It is preferred that A is unsubstituted phen-1,4-ylene ornaphth-1,4-ylene, or that it carries one or two substituents, moreespecially one, selected from --COOH, --SO₃ H, methyl, methoxy andchloro. Examples of preferred and especially preferred optionallysubstituted phenylene and naphthylene groups represented by A arephen-1,4-ylene, phen-1,3-ylene, 2-methylphen-1,4-ylene,2-methoxyphen-1,4-ylene, 3-methyl-phen-1,4-ylene,2-sulphophen-1,4-ylene, naphth-1,4-ylene and naphth-1,5-ylene.

The group of Formula (1a) may be free from ionisable groups or it maycarry an ionisable group. When the group of Formula (1a) is free fromionisable groups R⁶ is preferably one of the groups mentioned above inrelation to R⁶ other than --COOH --SO₃ H. When the group of Formula (1a)bears an ionisable group it is preferred that R⁶ is an ionisable groupe.g. R⁶ can be COOH; --SO₃ H; or alkyl, aryl, arylcarbonyl orarylsulphonyl, alkoxycarbonyl, alkoxysulphonyl, arylcarbonyl orarylsulphonyl, each of which is optionally substituted and each of whichcarries at least one ionisable group.

Preferably the group of Formula (1a) carries a carboxy group becausethis leads to dyes having a high optical density.

In the naphthylene group of Formula (1b) it is preferred that one of R²and R³ is H and the other is H, --COOH or --SO₃ H. Where one of R² andR³ is --COOH or --SO₃ H and the other is H, it is convenient to employ amixture of isomeric compounds in one of which R² is --COOH or --SO₃ Hand R³ is H and in the other R² is H and R³ is --COOH or --SO₃ H. It ispreferred that Z² is H, methyl, methoxy, --SO₃ H, --OH and morepreferably H.

In the phenylene group of Formula (1c) wherein Z¹ is --NZ³ Z⁴ it ispreferred that Z³ is H or C₁₋₄ -alkyl, such as methyl or ethyl. It isespecially preferred that Z³ is H. Where Z⁴ is alkyl this is preferablyC₁₋₄ -alkyl. Where Z⁴ is acyl this is preferably NH₂ CO--, R⁷ CO--or R⁷SO₂ --, wherein R⁷ is as hereinbefore defined. Where Z⁴ is other than H,and especially where it is acyl, Z³ is preferably H. It is especiallypreferred that --NZ³ Z⁴ is --NH₂.

In the phenylene group of Formula (1c) wherein Z¹ is optionallysubstituted alkyl or optionally substituted alkoxy, it is preferred thatZ¹ is C₁₋₄ -alkyl, e.g. methyl or ethyl, or C₁₋₄ -alkoxy, e.g. methoxyor ethoxy. It is especially preferred that Z¹ is H, methyl or methoxy.

In the phenylene group of Formula (1c) it is preferred that Z² is C₁₋₄-alkyl, C₁₋₄ -alkoxy, C₁₋₄ -alkylthio, --Cl, --H, --COOH or SO₃ H, morepreferably C₁₋₄ -alkyl, e.g. methyl or ethyl, or C₁₋₄ -alkoxy, e.g.methoxy or ethoxy. It is especially preferred that Z² is H, methyl ormethoxy.

The C₂₋₆ -alkylene group represented by B is preferably a C₂ - or C₃-alkylene group optionally substituted by a group listed below as anoptional substituent for R. It is especially preferred that B is --CH₂CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH₂ CH₂ --. It is preferred that T and T³are H.

Where R is alkyl this is preferably C₁₋₄ -alkyl and where R is aryl thisis preferably phenyl. Where the group represented by R is optionallysubstituted the optional substituents may be selected from C₁₋₄ -alkylor --COOH. Examples of atoms and groups represented by R are H, methyl,carboxymethyl, ethyl, carboxyethyl, phenyl, 3-carboxyphenyl,4-carboxyphenyl, 2,4-dicarboxyphenyl and 3,5-dicarboxyphenyl.

It is preferred that R¹ and R⁶ are each independently H, C₁₋₄ -alkyl,C₁₋₄ -alkyl-carbonyl or sulphonyl, C₁₋₄ -alkoxy-carbonyl or sulphonyl oraryl-carbonyl or sulphonyl, especially phenylcarbonyl, each of whichoptionally carries an ionisable group. Examples of such groups aremethyl, ethyl, acetyl, methylsulphonyl, methoxycarbonyl, ethoxycarbonyl,methoxysulphonyl and benzoyl. It is especially preferred that R¹ is H orC₁₋₄ -alkyl and R⁶ is H, C₁₋₄ -alkyl, C₁₋₄ -alkylcarbonyl, C₁₋₄-alkoxycarbonyl or benzoyl and more especially preferred that R¹ is Hand R⁶ is H, methyl, ethyl or acetyl. It is preferred that R⁴ and R⁵ areeach independently H or C₁₋₄ -alkyl and more especially preferred thatR⁴ and R⁵ are both H.

The ionisable group is preferably a group containing an ionisable Hatom, such as --COOH, --SO₃ H and --PO₂ (OH)₂, or a salt thereof.

When R, R¹, R⁴, R⁵, R⁷, Q¹, Q², Z¹, Z², Z³, Z⁴ or Z⁵ is or includesalkyl, this is preferably C₁₋₄ -alkyl, such as methyl, ethyl, propyl orbutyl, optionally substituted by C₁₋₄ -alkoxy, halo, especially chloro,--OH, --COOR⁸ or --SO₂ OR⁸ in which R⁸ is H, C₁₋₄ -alkyl or phenyl. WhenR⁷ is or includes optionally substituted aryl this is preferably phenyl,optionally substituted, preferably in the 2-, 3-, 4-, 2,4-, 3,4- or 3,5-positions, by a group or groups selected from C₁₋₄ -alkyl, C₁₋₄ -alkoxy,halo, --OH, --NH₂, --CN, --NO₂, --COOR⁸ and --SO₂ OR⁸.

When R⁶ is or includes optionally substituted alkyl, this is preferablyC₁₋₄ -alkyl, such as methyl, ethyl, propyl or butyl, optionallysubstituted by C₁₋₄ -alkoxy, halo, especially chloro, --OH, --COOR⁹ or--SO₂ OR⁹ in which R⁹ is C₁₋₄ -alkyl or phenyl. When R⁶ is or includesoptionally substituted aryl this is preferably phenyl, optionallysubstituted, preferably in the 2-, 3-, 4-, 2,4-, 3,4- or 3,5- positions,by a group or groups selected from C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halo, OH,NH₂, CN, NO₂, --COOR⁹ and --SO₂ OR⁹.

When Q¹ and Q², taken together with the N atom to which they areattached, form an optionally substituted 5- or 6-membered ring this ispreferably piperazinyl, morpholinyl or piperidinyl optionallysubstituted on a ring carbon atom by one or more groups represented byR⁴ and/or R⁵ or, in the case of piperazinyl, on the ring N atom by agroup represented by R⁶.

In a preferred compound of Formula (1),

    ______________________________________                                        J   is of Formula (1a) in which R.sup.4 and R.sup.5 are H and R.sup.6 is          H, C.sub.1-4 -alkyl,                                                          --CO--C.sub.1-4 -alkyl;                                                     A is phen-1,4-ylene or phen-1,3-ylene;                                        Y is of Formula (1b) in which R.sup.3 is H and R.sup.2 is H or --SO.sub.        3 H and                                                                      Z.sup.2 is H; or                                                             Y is of Formula (1c) in which Z.sup.1 is C.sub.1-4 -alkyl,                     C.sub.1-4 -alkoxy, di(COOH) or --NH.sub.2 ; Z.sup.2 is H,                     C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy and Z.sup.5 is H;                      R is H, C.sub.1-4 -alkyl, phenyl, phenylCOOH, phenyldi(COOH) or              B-NQ.sup.1 Q.sup.2 in which B is -                                              CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 -- or                      --CH.sub.2 CH(CH.sub.3)-- and Q.sup.1 and Q.sup.2 are each independentl        y                                                                            H, C.sub.1-4 -alkyl, or NQ.sup.1 Q.sup.2 is piperazinyl or 4-C.sub.1-4         -alkyl-piperazinyl;                                                          and R.sup.1, T and T.sup.1 are H.                                          ______________________________________                                    

In a second preferred compound of Formula (1),

    ______________________________________                                        J    is of Formula (1a) in which R.sup.4 and R.sup.5 are H and R.sup.6 is          --COOH,                                                                     --SO.sub.3 H, carboxy-C.sub.1-4 -alkyl or sulpho-C.sub.1-4 -alkyl;               A is phen-1,4-ylene or phen-1,3-ylene;                                    Y is of Formula (1b) in which R.sup.3 is H and R.sup.2 is H                    or --SO.sub.3 H and Z.sup.2 is --H; or                                       Y is of Formula (1c) in which Z.sup.1 is C.sub.1-4 -alkyl, C.sub.1-4             -alkoxy                                                                     or --NH.sub.2 and Z.sup.2 is H,                                               C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy and Z.sup.5 is H;                      R is H, C.sub.1-4 -alkyl, phenyl, carboxyphenyl, dicarboxyphenyl                   or --B--NQ.sup.1 Q.sup.2 in which B is                                    --CH.sub.2 CH.sub.2 --, --CH.sub.2 CH(CH.sub.3)--, or --CH.sub.2                CH.sub.2 CH.sub.2 --                                                        and Q.sup.1 and Q.sup.2 are each                                              independently H, C.sub.1-4 -alkyl, or NQ.sup.1 Q.sup.2 is piperazinyl             or 4-C.sub.1-4 -alkyl-piperazinyl; and                                    R.sup.1, T & T.sup.1 are H.                                                ______________________________________                                    

Although the compound of Formula (1) may be in the free acid form, thatis a form in which each ionisable group, such as --COOH or --SO₃ H is inthe free acid form as hereinbefore shown, it is preferably in the formof a salt with one or more cations selected from an alkali metal,ammonium and optionally substituted ammonium cation. Preferably thecation is ammonium or optionally substituted C₁₋₄ -alkylammonium. Apreferred cation consists of a nitrogen atom having four substituentsselected from H, C₁₋₄ -alkyl and hydroxy-C₁₋₄ -alkyl, for example mono-,di-, tri- and tetra-(C₁₋₄ -alkyl)-ammonium and mono-, di-, tri- andtetra-(hydroxy-C₁₋₄ -alkyl)ammonium. It is especially preferred that thecompound of Formula (1), (2) or (3) is a salt with an ammonium (i.e. NH₄⁺), or a mono- or poly-, methyl-, ethyl- or hydroxyethyl-ammonium cationor with a mixture of two or more cations, especially a mixture of alkalimetal, (such as sodium) and optionally substituted ammonium cations.Examples of optionally substituted C₁₋₄ -alkylammonium cations includemono-, di-, tri- and tetra-methylammonium, mono-, di-, tri- and tetra-ethylammonium, and mono-, di-, tri- and tetra-(2-hydroxyethyl)-ammonium.

The present compounds can be prepared by diazotising an amine of formulaVS--A--NH₂, in which VS-- is a vinylsulphone group (or a precursorthereof), preferably below 5° C. using a nitrite and mineral acid,coupling with a substituted aminonaphthalene carrying groups R², R³ andZ² or with a substituted aniline carrying groups Z¹, Z² and Z⁵ to give amonoazo compound, diazotising the monoazo compound and coupling with aGamma Acid or 2R Acid derivative of Formula (2): ##STR6## and convertingthe vinylsulphone group (or precursor thereof) on A into a group J--CH₂CH₂ SO₂ -- by reaction with a piperazine of formula J--H.

The present compounds may also be prepared by converting thevinylsulphone group (or precursor thereof) on A into a group J--CH₂ CH₂SO₂ -- by reaction with a piperazine of formula J--H after the firstdiazotisation followed by the second diazotisation and coupling with thecompound of Formula (2).

Compounds of Formula (2) in which R is other than H may be preparedusing the Bucherer reaction in which1-hydroxy-3-sulpho-7-hydroxy-naphthalene or1-hydroxy-3,6-disulpho-7-hydroxynaphthalene is reacted with an amine, R¹--NH--R, in the presence of an alkali metal or ammonium sulphite andbisulphite (e.g. Na₂ SO₃ and NaHSO₃) with heating, preferably from60-100° C. and especially 70-90° C. Where R¹ is acyl in the compound ofFormula (1), the amine R¹ --NH--R may be replaced by an amine, H₂ N--R,and the acyl group incorporated subsequently by acylation of thesecondary amino group, --NH--R. In the above processes J, A, R, R¹, R²,R³, Z¹, Z², Z⁵, T and T¹ are as hereinbefore defined.

The present invention relates not only to a compound of Formula (1) butalso to a composition comprising two or more such compounds. An exampleof such a composition is a mixture containing two compounds of Formula(1) in which Y is of Formula (1b) in one of which R³ is H and R² is--COOH or --SO₃ H and in the other R³ is --COOH or --SO₃ H and R² is H.It is preferred that such a composition contains two compounds ofFormula (1) in a weight-to-weight ratio of 99:1 to 1:99, more preferably90:10 to 10:90, especially 80:20 to 20:80, more especially 60:40 to40:60.

The compound or composition of the present invention is convenientlysynthesised in the form of an alkali metal, e.g. sodium salt. This maybe converted wholly or partially into its ammonium or optionallysubstituted C₁₋₄ -alkylammonium salt by dissolving in water the compoundin the form of a salt with an alkali metal, acidifying the solution witha mineral acid, e.g. hydrochloric acid, separating of the precipitatedcompound in free acid form, suspending it in water, adjusting thesuspension to pH 9-9.5 with ammonia or an optionally substituted C₁₋₄-alkylamine to form the water soluble ammonium or substituted ammoniumsalt, and removing alkali metal chloride ions by dialysis. Alternativelythe alkali metal ion may be partially or wholly exchanged for anoptionally substituted ammonium ion by a conventional ion exchangemethod.

It will be understood that the present invention covers all tautomericforms of a compound of Formula (1), for example the tautomericequivalent of Formula (1) in which the hydroxy group on the naphthalenering is in the keto form.

A compound or composition of the present invention, especially in theform of its ammonium or optionally substituted C₁₋₄ -alkylammonium salt,is useful as a black colorant for the preparation of inks. In the formof a salt with an alkali metal or ammonium ions it has good solubilityin water and aqueous media and good water fastness and is capable ofgiving a strong black print with high-water-fastness on plain paper. Theammonium salt form of the dye is especially preferred because it givesprints of especially high water-fastness.

Compounds of Formula (1) in which Y is of Formula (1b) wherein R³ is Hand R² is H or --SO₃ H and of Formula (1) in which Y is of Formula (1c)wherein Z¹ is NH₂ or C₁₋₄ - alkoxy especially methoxy and Z² is alkoxy,especially methoxy, in the form of their ammonium or substitutedammonium salts, perform especially well as ink colorants.

The compound and composition are versatile, exhibiting high waterfastness and rapid fixation on alkaline, neutral and acid papers, goodsolubility in aqueous ink media and good strong black prints withminimal bronzing.

According to a further feature of the present invention there isprovided an ink comprising a compound or a composition according to thepresent invention and a liquid medium, preferably an aqueous medium. Itis preferred that the compound or composition is completely dissolved inthe liquid medium to form a solution.

The ink preferably contains from 0.5% to 20%, more preferably from 0.5%to 15%, and especially from 1% to 3%, by weight of the compound orcomposition, based on the total weight of the ink. Although many inkscontain less than 5% by weight of colorant, it is desirable that thecompound or composition has a water solubility of around 10% or more toallow the preparation of concentrates from which more dilute inks can beprepared and to minimise the chance of precipitation of colorant ifevaporation of solvent occurs during use of the ink.

The liquid medium preferably comprises water or a mixture of water andone or more water-soluble organic solvents. The weight ratio of water toorganic solvent(s) is preferably from 99:1 to 1:99, more preferably from99:1 to 50:50 and especially from 95:5 to 80:20. The water-solubleorganic solvent(s) is preferably selected from C₁₋₄ -alkanols such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol or isobutanol; amides such as dimethylformamide ordimethylacetamide; ketones or ketone-alcohols such as acetone ordiacetone alcohol; ethers such as tetrahydrofuran or dioxane; oligo- orpoly-alkyleneglycols such as diethylene glycol, triethylene glycol,polyethylene glycol or polypropylene glycol; alkyleneglycols orthioglycols containing a C₂₋₆ -alkylene group such as ethylene glycol,propylene glycol, butylene glycol, pentylene glycol or hexylene glycoland thiodiglycol; polyols such as glycerol or 1,2,6-hexanetriol; C₁₋₄-alkylethers of polyhydric alcohols such as 2-methoxy-ethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-[2-(2-methoxy-ethoxy) ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]ethanol; heterocyclic ketones, such as2-pyrrolidone and N-methyl-2-pyrrolidone; or mixtures containing two ormore of the aforementioned water-soluble organic solvents, for examplethiodiglycol and a second glycol or diethylene glycol and 2-pyrrolidone.

Preferred water-soluble organic solvents are 2-pyrrolidone;N-methyl-2-pyrrolidone; C₂₋₆ -alkylene- and oligo-(C₂₋₆-alkylene)glycols, such as ethyleneglycol, diethyleneglycol,triethyleneglycol; and C₁₋₄ -alkyl ethers of polyhydric alcohols andglycols such as 2-methoxy-2-ethoxy-2-ethoxyethanol; and poly-(C₂₋₄-alkyleneglycol)s with a molecular weight of up to 500. A preferredspecific solvent mixture is a binary or ternary mixture of water anddiethylene glycol and/or, 2-pyrrolidone or N-methyl-2-pyrrolidone inweight ratios 75-95:25-5 and 60-80:0-20:0-20 respectively.

Examples of suitable ink media are given in U.S. Pat. No. 4,963,189,U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP 4,251,50A.

A further aspect of the present invention provides a process forprinting a substrate with an ink using an ink jet printer, characterisedin that the ink contains at least one compound of Formula (1) ashereinbefore described.

A suitable process for the application of an ink as hereinbeforedescribed comprises forming the ink into small droplets by ejection froma reservoir through a small orifice so that the droplets of ink aredirected at a substrate. This process is commonly referred to as ink jetprinting, and preferred ink jet printing processes for the present inksare piezoelectric ink jet printing and thermal ink jet printing. Inthermal ink jet printing, programmed pulses of heat are applied to theink in the reservoir by means of a resistor adjacent to the orifice,during relative movement between the substrate and the reservoir.

According to a still further aspect of the present invention there isprovided a substrate printed with a compound of Formula (1).

A preferred substrate is an overhead projector slide or a cellulosicsubstrate, especially cotton or paper, especially plain and treatedpapers, which may have an acid, alkaline or neutral character.

The preferred ink used in the process is as hereinbefore described.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

Preparation of the Compound of Formula (A) ##STR7## Stage 1

4-(4-[2-{4-methylpiperazinyl}ethylsulponyl]phenylazo)-2-methoxy-5-methylaniline

To a stirred suspension of4-(2'-(4"-methylpiperazinyl)ethylsulphonyl)-aniline (56.6 g) inice/water (1 l) was added sufficient 2N NaOH solution to raise the pH to8 and bring about a clear solution, followed by NaNO₂ (15.2 g). Thismixture was then added to a solution of conc HCl (50 ml) in ice/water(150 g) at 0-10° C. When the addition was complete the resultant diazosuspension was stirred at 0-10° C. for 2 hour and residual HNO₂destroyed by addition of sulphamic acid.

2-Methoxy-5-methylaniline (27.4 g) was dissolved in ethanol (500 ml) andadded to the above diazo suspension at 0-10° C. Water was added to raisethe total volume to 2.5 l and the mixture was stirred for 18 hoursallowing the temperature to rise to 20° C. The precipitated product wasfiltered off and the filter cake washed with water and dried at 70° C.

Stage 2

N-(2-Piperazinylethyl)-Gamma acid

A mixture of 1-(2-aminoethyl)piperazine (387 g),1,7-dihydroxy-3-sulpho-naphthalene (285 g), NaHSO₃ (280 g) and water(1.251) was stirred and heated at 85-90° C. for 18 hours. The solutionwas filtered from a little insoluble material and the filtrate cooled to10-20° C. Concentrated HCl was slowly added to adjust the pH to 2 andthe reaction mixture then salted to 10% with NaCl. The mixture wasstirred for 6 hours and the product filtered off, washed with 20% NaClsolution and dried at 60° C. (yield 215 g).

Stage 3

The product of Stage 1 (23 g) was dissolved in water (800 ml) at roomtemperature by the addition of sufficient 2N NaOH to raise the pH to9-10 and NaNO₂ (5.5 g) was added. This solution was added over a periodof 10 minutes to a mixture of concentrated HCl (30 ml) and ice-water(150 ml), maintaining the temperature at 0-10° C. After 3 hours at 0-10°C. excess HNO₂ was destroyed by the addition of sulphamic acid to give adiazo solution.

N-(2-piperazinylethyl)-Gamma Acid (30.2 g) from Stage 2 was dissolved inwater (500 ml) by the addition of 2N NaOH to pH 9.0 followed by Na₂ CO₃and the solution was cooled to 0-10° C. The diazo solution was thenadded slowly over 10 minutes, maintaining the temperature at 0-10° C. bythe addition of ice and the pH at 9-10 by addition of 2N NaOH solution.The mixture was then stirred for 18 hours allowing the temperature torise to 20° C. The suspension was then heated to 70° C., salted to 20%with NaCl and the pH adjusted to 6 with 2N HCl. The precipitated product(of Formula (A) in Na salt form) was filtered and washed with 25% NaClsolution.

Stage 4

The filter paste from Stage 3 was dissolved in water (1 l) by adjustingthe pH to 9-10 with conc NH₄ OH. It was then slowly added to 2N HCl (2l). The compound of Formula (A), in free acid form, was filtered andwashed with 1N HCl. This procedure was repeated twice before the filterpaste was added to water (500 ml) and the solid completely dissolved byadjusting to pH 9-10 with conc NH₄ OH. The solution was dialysed untilCl⁻ could no longer be detected, screened through a B 0.45μm filter, andthe product of Formula (A) (as ammonium salt) isolated by evaporationand dried at 70° C.

The compound of Formula (A) (ammonium salt) (2.5 parts) was added to amixture of water (90 parts) and diethylene glycol (10 parts) and printedonto plain paper substrate using a thermal ink jet printer. The printhad a bluish-black shade with excellent water fastness and a fast rateof fixation to the substrate.

EXAMPLE 2

Example 1 was repeated except that in place of4-(2'-(4"-methylpiperazinyl) ethylsulphonyl)-aniline there was used4-(2'-(4"-carboxymethyl piperazinyl)ethylsulphonyl)aniline.

The resultant black dye was made into ink using the formulationdescribed in Example 1 and was found to print plain paper a bluish-blackshade with excellent water-fastness and rate of fixation.

EXAMPLE 3

Preparation of ##STR8## Stage 1

Sodium nitrite (38 g, 0.55 mol) was added to a stirred suspension of4-(β-sulphatoethylsulphonyl aniline ("Component A", 140.5 g, 0.5 mol) inwater (1.5 L), at pH 6.5-7.0. This mixture was cooled to below 5° C. andconcentrated HCl (125 ml) was added dropwise, maintaining temperature at0-5° C. The resulting cloudy yellow mixture was left to stir, at 0-10°C., pH ˜2, for a further 3 hrs. Excess nitrous acid was then destroyedby adding sulfamic acid to give a diazo suspension. 2,5-Dimethoxyaniline("Component B", 76.5 g, 0.5 mol) was dissolved in methylated spirits(750 ml) and cooled to <5° C. To this stirred solution the above diazosuspension was added in a slow stream, at 0-10° C. A red mixture wasobtained. This was further stirred at 0-10° C. for 2 hrs before allowingthe mixture to warm to room temperature and leaving it to stirovernight. The next morning stirring was stopped and the mixture wasleft to settle for half an hour before filtering. The filter cake waswashed with saturated brine solution (500 ml) and then left to dry inthe vacuum oven (60° C.) until constant weight. The solid was thenground to give a monoazo compound in powdered form (187.5 g, 0.42 mol).

Stage 2

A solution of N-methylpiperazine ("Component C", 41 g, 0.41 mol) inwater (500 ml) was heated to 65 ° C. To this stirred solution, theproduct from stage 1 (90 g, 0.2 mol), was added portionwise. Theresultant mixture was stirred at this temperature and pH 9 for 2 hoursbefore stopping the stirring and allowing to cool to room temperatureovernight. Water was removed under vacuum to leave a tar. Concentratedammonia was added to the tar to give a brittle solid. The solid wasfiltered-off, washed with a little water and dried in the oven, at 60°C. until constant weight (64.7 g, 0.15 mol).

Stage 3

The product from stage 2 (20 g, 0.045 mol) was dissolved in water (300ml) and concentrated HCl (20 ml) and then cooled to 5° C. To thisstirred solution, sodium nitrite (3.4 g, 0.049 mol) in water (50 ml),was added slowly, maintaining the temperature at 0-10° C. The mixturewas stirred for a further 2 hours at this temperature. Excess nitrousacid was then destroyed by the careful addition of sulfamic acid to giveazo solution 2. 1-Hydroxy-7-amino-3,6-disulphonaphthalene ("componentD") (15.6 g, 0.046 mol) was dissolved in water (150 ml), pH 9.5 andcooled to 5° C. Azo solution 2 was then added slowly to this stirredsolution, maintaining the above conditions.

A black mixture was obtained and this was further stirred at 5-10° C.for 2 hours before leaving to stir overnight allowing to warm to roomtemperature. The pH was lowered to ˜3.5 (using concentrated HCl) and theresultant precipitate was filtered-off, dried then redissolved in waterand ammonia (pH 10). The solid was re-precipitated by pouring thesolution into a stirring 4M HCl solution (1:1). The precipitate wasfiltered-off and dried on a buchner funnel until damp. The process ofmaking the ammonium salt was repeated. Finally the solid was redissolvedin water/ammonia and dialysed in a dialysis tube to remove chlorideions. The resultant solution was filtered through GF/F paper and driedin an oven at 60° C. The title product was obtained in a yield of 26.3 g(0.03 mol).

EXAMPLES 4 to 52

The general method of Example 3 was repeated except that in place ofcomponent A, B, C or D there was used the component listed in Table Abelow. Where no component is specified in Table A, the component usedwas exactly the same as in Example 3.

                  TABLE A                                                         ______________________________________                                        Ex-   Compo-   Compo-     Compo-   Compo-                                       ample nent A nent B nent C nent D                                           ______________________________________                                         4             1-amino             1-hydroxy-7-(4-                                naphthalene  carboxyphenyl                                                      amino)-3-                                                                     sulpho                                                                        naphthalene                                                                5  1-amino-7- 2-methyl 1-hydroxy-7-(4-                                         sulpho piperazine carboxyphenyl                                               naphthalene  amino)-3-                                                          sulpho                                                                        naphthalene                                                                6  1-amino-7- N-formyl 1-hydroxy-7-(4-                                         sulpho piperazine carboxyphenyl                                               naphthalene  amino)-3-                                                          sulpho                                                                        naphthalene                                                                7  1-amino N-(2-hydroxy 1-hydroxy-7-(4-                                        naphthalene ethyl) carboxyphenyl                                               piperazine amino)-3-                                                           sulpho                                                                        naphthalene                                                                8  1-amino N-formyl 1-hydroxy-7-                                               naphthalene piperazine amino-3,6-                                               disulphonaphth                                                                alene                                                                      9  1-amino N-(2-hydroxy 1-hydroxy-7-                                           naphthalene ethyl) amino-3,6-                                                  piperazine disulphonaphth                                                      alene                                                                     10  1-amino 2-methyl 1-hydroxy-7-                                               naphthalene piperazine amino-3,6-                                               disulphonaphth                                                                alene                                                                     11    1-hydroxy-7-(4-                                                             carboxyphenyl                                                                 amino)-3-                                                                     sulpho                                                                        naphthalene                                                               12   N-acetyl 1-hydroxy-7-(4-                                                    piperazine carboxyphenyl                                                       amino)-3-                                                                     sulpho                                                                        naphthalene                                                               13   N-(2- 1-hydroxy-7-(4-                                                       hydroxyethyl) carboxyphenyl                                                   piperazine amino)-3-                                                           sulpho                                                                        naphthalene                                                               14  2-methoxy-5- N-acetyl 1-hydroxy-7-(4-                                       methyl aniline piperazine carboxyphenyl                                         amino)-3-                                                                     sulpho                                                                        naphthalene                                                               15  2-methoxy-5-  1-hydroxy-7-(4-                                               methyl aniline  carboxyphenyl                                                   amino)-3-                                                                     sulpho                                                                        naphthalene                                                               16   N-carboxy 1-hydroxy-7-(4-                                                   methylene carboxyphenyl                                                       piperazine amino)-3-                                                           sulpho                                                                        naphthalene                                                               17  2-methoxy-5-  1-hydroxy-7-(4-                                               amino aniline  carboxyphenyl                                                    amino)-3-                                                                     sulpho                                                                        naphthalene                                                               18  2-methoxy-5-  1-hydroxy-7-                                                  amino aniline  amino-3-                                                         sulpho                                                                        naphthalene                                                               19  1-amino  1-hydroxy-7-                                                       naphthalene  amino-3-                                                           sulpho                                                                        naphthalene                                                               20   N-(2-hydroxy 1-hydroxy-7-                                                   ethyl) amino-3-                                                               piperazine sulpho                                                              naphthalene                                                               21    1-hydroxy-7-                                                                amino-3-                                                                      sulpho                                                                        naphthalene                                                               22  2-methoxy-5- N-(2-hydroxy 1-hydroxy-7-                                      amino aniline ethyl) amino-3-                                                  piperazine sulpho                                                              naphthalene                                                               23  1-amino-7-  1-hydroxy-7-                                                    sulpho  amino-3-                                                              naphthalene  sulpho                                                             naphthalene                                                               24  2-methoxy-5-  1-hydroxy-7-                                                  acetamido  amino-3-                                                           aniline  sulpho                                                                 naphthalene                                                               25  2-methoxy-5-  1-hydroxy-7-(2-                                               methyl aniline  [1-piperazinyl]                                                 ethylamino)3-                                                                 sulpho                                                                        naphthalene                                                               26  2-sulpho-5-  1-hydroxy-7-                                                   amino aniline  amino-3-                                                         sulpho                                                                        naphthalene                                                               27  1-amino N-carboxy 1-hydroxy-7-(4-                                           naphthalene methylene carboxy                                                  piperazine phenylamino)-                                                       3-sulpho aniline                                                          28  1-amino-7- N-carboxy 1-hydroxy-7-(4-                                        sulpho methylene carboxy                                                      naphthalene piperazine phenylamino)-                                            3-sulpho                                                                      naphthalene                                                               29  1-amino N-carboxy 1-hydroxy-7-                                              naphthalene methylene amino-3-                                                 piperazine sulpho                                                              naphthalene                                                               30   N-carboxy 1-hydroxy-7-(2-                                                   methylene [1-piperazinyl]                                                     piperazine ethylamino)3-                                                       sulpho                                                                        naphthalene                                                               31   N-carboxy 1-hydroxy-7-N-                                                    methylene (2-piperazinyl-                                                     piperazine ethyl)-3-sulpho                                                     naphthalene                                                               32  2-acetamido-5- N-carboxy 1-hydroxy-7-(4-                                    methoxy methylene carboxyphenyl                                               aniline piperazine amino)-3-                                                    sulpho                                                                        naphthalene                                                               33   N-carboxy 1-hydroxy-7-                                                      methylene dimethylamino-                                                      piperazine 3-sulpho                                                            naphthalene                                                               34  1-amino N-carboxy 1-hydroxy-7-                                              naphthalene methylene dimethylamino-                                           piperazine 3-sulpho                                                            naphthalene                                                               35  1-amino N-carboxy 1-hydroxy-7-(2-                                           naphthalene methylene [1-piperazinyl]                                          piperazine ethylamino)3-                                                       sulpho                                                                        naphthalene                                                               36  5-amino-2- N-carboxy 1-hydroxy-7-(N-                                        methoxy methylene carboxyphenyl                                               aniline piperazine amino)-3-                                                    sulpho                                                                        naphthalene                                                               37  2-methoxy-5- N-carboxy 1-hydroxy-7-                                         acetamido methylene amino-3-                                                  aniline piperazine sulpho                                                       naphthalene                                                               38  2-amino-5- N-carboxy 1-hydroxy-7-                                           methoxy methylene amino-3-                                                    aniline piperazine sulpho                                                       naphthalene                                                               39  2-methoxy-5- N-carboxy 1-hydroxy-7-(2-                                      acetamido methylene [1-piperazinyl]                                           aniline piperazine ethylamino)3-                                                sulpho                                                                        naphthalene                                                               40  2-methoxy-5- N-carboxy 1-hydroxy-7-(2-                                      amino aniline methylene [1-piperazinyl]                                        piperazine ethylamino)3-                                                       sulpho                                                                        naphthalene                                                               41 3-(β 2-methoxy-5- N-acetyl 1-hydroxy-7-(4-                           sulphato methyl aniline piperazine carboxyphenyl                                ethyl   amino)-3-                                                             sulphonyl)   sulpho                                                           aniline   naphthalene                                                        42 3-(β  N-acetyl 1-hydroxy-7-(4-                                       sulphato  piperazine carboxyphenyl                                              ethyl   amino)-3-                                                             sulphonyl)   sulpho                                                           aniline   naphthalene                                                        43 3-(β 2-methoxy-5- N-(2-hydroxy 1-hydroxy-7-(4-                       sulphato methyl aniline ethyl) carboxyphenyl                                    ethyl  piperazine amino)-3-                                                   sulphonyl)   sulpho                                                           aniline   naphthalene                                                        44 3-(β  N-(2-hydroxy 1-hydroxy-7-(4-                                   sulphato  ethyl) carboxyphenyl                                                  ethyl  piperazine amino)-3-                                                   sulphonyl)   sulpho                                                           aniline   naphthalene                                                        45 3-(β   1-hydroxy-7-(4-                                               sulphato   carboxyphenyl                                                        ethyl   amino)-3-                                                             sulphonyl)   sulpho                                                           aniline   naphthalene                                                        46 3-(β 2-methoxy-5-  1-hydroxy-7-(4-                                   sulphato amino aniline  carboxyphenyl                                           ethyl   amino)-3-                                                             sulphonyl)   sulpho                                                           aniline   naphthalene                                                        47 3-(β 2-methoxy-5-  1-hydroxy-7-                                      sulphato amino aniline  amino-3-                                                ethyl   sulpho                                                                sulphonyl)   naphthalene                                                      aniline                                                                      48 3-(β   1-hydroxy-7-(4-                                               sulphato   carboxy                                                              ethyl   phenylamino)-                                                         sulphonyl)   3-sulpho                                                       6-meth-   naphthalene                                                           oxy                                                                           aniline                                                                      49 3-(β  N-(2-hydroxy 1-hydroxy-7-                                      sulphato  ethyl) amino-3-                                                       sulphonyl)  piperazine sulpho                                               6-   naphthalene                                                                methoxy                                                                       aniline                                                                      50 3-(β  N-carboxy 1-hydroxy-7-(4-                                      sulphato  methylene carboxy                                                     ethyl  piperazine phenyl)-3-                                                  sulphonyl)   sulpho                                                         6-   naphthalene                                                                methoxy                                                                       aniline                                                                      51 3-(β 1-amino N-carboxy 1-hydroxy-7-(4-                               sulphato naphthalene methylene carboxy                                          ethyl  piperazine phenyl)-3-                                                  sulphonyl)   sulpho                                                         6-   naphthalene                                                                methoxy                                                                       aniline                                                                      52 3-(β 1-amino N-carboxy 1-hydroxy-7-                                  sulphato naphthalene methylene amino-3-                                         ethyl  piperazine sulpho                                                      sulphonyl)   naphthalene                                                    6-                                                                              methoxy                                                                       aniline                                                                    ______________________________________                                    

By way of illustration the dyes resulting from Examples 4 to 52 had thestructures shown on the following pages. These structures show theskeleton of the dyes and hydrogen atoms are not shown. ##STR9## InkExamples

Inks may be prepared according to the formulations described in Tables Iand II wherein the Dye mentioned in the first column is the dyedescribed in the above Example of the same number. Numbers quoted in thesecond column onwards refer to the number of parts of the relevantingredient and all parts are by weight.

The inks may be applied to paper using a thermal or piezo ink jetprinter to give black images.

The following abbreviations are used:

PG=propylene glycol

DEG=diethylene glycol

NMP=N-methyl pyrollidone

DMK=dimethylketone

IPA=isopropanol

MEOH-methanol

2P=2-pyrollidone

MIBK=methylisobutyl ketone

P12=propane-1,2-diol

BDL=butane-2,3-diol

CET=cetyl ammonium bromide

PHO=Na₂ HPO₄ and

TBT=tertiary butanol

TDG=thiodiglycol

                                      TABLE I                                     __________________________________________________________________________       Dye                    Na                                                    Dye Content Water PG DEG NMP DMK NaOH Stearate IPA MEOH 2P MIBK             __________________________________________________________________________     1 2.0 80  5    6  4                 5                                           2 3.0 90  5 5  0.2                                                            3 10.0  85 5  2 2    5 1                                                      4 2.1 91  8        1                                                          5 3.1 86 5     0.2 4   5                                                      6 1.1 81   9  0.5 0.5   9                                                     7 2.5 60 4 15  3 3   6 10  5 4                                                8 5   65  20      10                                                          9 2.4 75 5 4  5    6  5                                                      10 4.1 80 3 5 2 10   0.3                                                      11 3.2 65  5 4 6   5 4 6 5                                                    12 5.1 96        4                                                            13 10.8  90 5      5                                                          14 10.0  80 2 6 2 5   1  4                                                    15 1.8 80  5       15                                                         16 2.6 84   11       5                                                        17 3.3 80 2   10     2  6                                                     18 12.0  90    7 0.3  3                                                       19 5.4 69 2 20  2 1     3 3                                                   20 6.0 91   4      5                                                        __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________       Dye                                                                          Dye Content Water PG DEG NMP CET TBT TDG BDL PHO 2P PI2                     __________________________________________________________________________    21 3.0 80  15       0.2            5                                            22 9.0 90  5      1.2  5                                                      23 1.5 85 5 5   0.15 5.0 0.2                                                  24 2.5 90  6 4      0.12                                                      25 3.1 82 4 8  0.3      6                                                     26 0.9 85  10      5 0.2                                                      27 8.0 90  5 5   0.3                                                          28 5.0 70  10  4    1  4 11                                                   29 2.2 75 4 10  3    2  6                                                     30 10.0  91   6      3                                                        31 9.0 76  9 7  3.0    0.95 5                                                 32 5.0 78 5 11        6                                                       33 5.4 86   7      7                                                          34 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5                                           35 2.0 90  10                                                                 36 2   88      10                                                             37 5   78   5   12     5                                                      38 8   70 2  8   15     5                                                     39 10   80      8     12                                                      40 10   80  10                                                              __________________________________________________________________________

We claim:
 1. A compound of Formula (1) or a salt thereof: ##STR10##wherein: J is a group of the Formula (1a): ##STR11## wherein: ##STR12##wherein

    ______________________________________                                        R.sup.2 & R.sup.3                                                                   each independently is H, --COOH or --SO.sub.3 H;                          Z.sup.1 & Z.sup.5 each independently is H, optionally substituted                 alkyl, optionally                                                          substituted alkoxy or --NZ.sup.3 Z.sup.4 ;                                   Z.sup.2 is H, halo, --COOH, --SO.sub.3 H, --OH, optionally substituted              alkyl, optionally substituted alkoxy or optionally substituted                alkylthio;                                                              Z.sup.3 is H or optionally substituted alkyl;                                 Z.sup.4 is H, optionally substituted alkyl or acyl;                           R.sup.1 is H, optionally substituted alkyl, alkylcarbonyl, alkylsulphony          l,                                                                         alkoxycarbonyl, alkoxysulphonyl, arylcarbonyl or arylsulphonyl;                   T & T.sup.1 each independently is H or --SO.sub.3 H;                     R is H, optionally substituted alkyl, optionally substituted aryl,                  or a group --B--NQ.sup.1 Q.sup.2 ;                                      B is optionally substituted C.sub.2-6 -alkylene; and                          Q.sup.1 & each independently is H, optionally substituted C.sub.1-4               -alkyl or                                                                 Q.sup.2 Q.sup.1 and Q.sup.2 together with the N atom to which they are            attached                                                                   form an optionally substituted 5- or 6-membered ring.                      ______________________________________                                    


2. A compound according to claim 1 wherein R⁶ is --COOH, --SO₃ H, alkyl,aryl, alkylcarbonyl, alkylsulphonyl, alkoxycarbonyl, alkoxysulphonyl,arylcarbonyl or arylsulphonyl each of which is optionally substitutedand each of which carries at least one ionisable group.
 3. A compoundaccording to claim 1 wherein J is a group of the Formula (1a) and isfree from ionisable groups and R⁶ is H or optionally substituted alkyl,aryl, alkylcarbonyl, alkylsulphonyl, alkoxycarbonyl, alkoxysulphonyl,arylcarbonyl or arylsulphonyl.
 4. A composition comprising two or morecompounds of Formula (1), as defined in any one of claims 1 to
 3. 5. Anink comprising a liquid medium and a compound of Formula (1), as definedin any one of claims 1 to
 3. 6. An ink comprising a liquid medium and acomposition according to claim
 4. 7. An ink according to claim 5 or 6wherein the liquid medium comprises a mixture of water and one or morewater-soluble organic solvents.
 8. A process for printing a substratewith an ink using an ink jet printer which comprises ink from the jetprinter onto a substrate the ink is as defined in claim 5, 6 or
 7. 9. Aprocess according to claim 8 wherein the substrate is paper.
 10. Asubstrate printed with at least one compound of Formula (1), as definedin claim 1.